3-nitroisoxazoles and their use in the protection of materials

ABSTRACT

The 3-nitroisoxazoles of the formula (I)  
                 
 
     in which R 1  and R 2  are each as defined in the description, some of which are known, are highly suitable for use as biocides for protecting industrial materials.

FIELD OF THE INVENTION

[0001] The present invention relates to novel 3-nitroisoxazoles, aprocess for their preparation and to the use of novel and known3-nitroisoxazoles as biocides for protecting industrial materials.

BACKGROUND OF THE INVENTION

[0002] Some 3-nitroisoxazoles having alkyl, aryl, hetaryl, alkinyl andalkoxycarbonyl radicals are known; a biological action of the compoundsmentioned has not been described. (K. Baum. J. Org. Chem. 1985, 50,2736; K. Kim, Tetrahedron Lett. 1996, 37, 7791; K. Eiter,Naturwissenschaften 1972, 59, 468; E. Duranti, Tetrahedron Lett. 1973,7, 485).

[0003] 3,5-Dinitroisoxazoles are known; here, too, an antibacterialaction has not been described (D. T. Corner, Acta Crystallogr., Sect. C.Cryst. Struct. Commun. 1987, 43, 2011). Specifically substituted3-nitroisoxazole-5-carboxaldehyde derivatives are known and in somecases have weak to moderate antibacterial actions (E. Duranti II FarmacoEd. Sc. 1987, 42, 299).

SUMMARY

[0004] The invention relates to a method comprising treating a microbeor a habitat of the microbe with a compound of the formula (I)

[0005] wherein R¹ and R² independently of one another each representhydrogen, halogen, nitro, cyano, or represent in each case an optionallysubstituted alkyl, alkenyl, alkinyl or aryl, such that the compound isallowed act on the microbe or its habitat.

[0006] In one embodiment, Applicants' invention is directed to amicrobicidal composition comprising: (A) a compound of the formula (I)

[0007] wherein R¹ and R² independently of one another each representhydrogen, halogen, nitro, cyano, or represent in each case an optionallysubstituted alkyl, alkenyl, alkinyl or aryl, (B) solvents or diluentsand, (C) optionally processing auxiliaries, or active compounds, ormixtures thereof.

[0008] In one embodiment, Applicants' invention relates to a process forpreparing a compound of the formula (I)

[0009] wherein R¹ and R² independently of one another each representhydrogen, halogen, nitro, cyano, or represent in each case an optionallysubstituted alkyl, alkenyl, alkinyl or aryl,

[0010] in which the process comprising reacting (i) a compound of theformula (II)

R²—C≡C—R¹  (II)

[0011]  wherein R¹ and R² are each as defined above with (ii)tetranitroethylene, and optionally in the presence of a diluent.

[0012] In another embodiment, Applicants' invention relates to a processfor preparing a compound of the formula (I)

[0013] wherein R¹ is hydrogen, halogen, nitro, cyano, or represent ineach case an optionally substituted alkyl, alkenyl, alkinyl or aryl, R²represents hydrogen. In this embodiment, the process comprises reacting(i) a compound of the general formula (III)

X—CH₂—C≡C—R¹  (III)

[0014] in which R¹ is as defined above and X represents a leaving group,preferably bromine, iodine, chlorine, tosylate or mesylate with (ii)metal nitrites, optionally, in the presence of diluents. These and otherfeatures, aspects, and advantages of the present invention will becomebetter understood with reference to the following description andappended claims.

DESCRIPTION

[0015] It has now been found that 3-nitroisoxazoles of the generalformula (I)

[0016] in which R¹ and R² independently of one another each representhydrogen, halogen, nitro, cyano, or represent in each case optionallysubstituted alkyl, alkenyl, alkinyl or aryl, have excellent bactericidalaction. Owing to their antibacterial and antifungal action, thecompounds of the formula (I), alone or in a mixture with one another,are particularly suitable for controlling microorganisms in and onindustrial materials.

[0017] Moreover, the compounds of the formula (I) have good long-termaction and stability in industrial materials.

[0018] The formula (I) provides a general definition of the compoundswhich can be used according to the invention. Preference is given tousing compounds of the formula (I) in which

[0019] R¹ and R² independently of one another each represent hydrogen,halogen, cyano, nitro, or represent in each case straight-chain orbranched C₁-C₈-alkyl, C₂-C₈-alkenyl or C₂-C₈-alkinyl, each of which isoptionally mono- or polysubstituted by identical or differentsubstituents from the group consisting of halogen, nitro, cyano, aryl,aryloxy, C₁-C₆-alkoxy, which is optionally mono- to nonasubstituted byidentical or different halogens, C₁-C₆-alkylthio, which is optionallymono- to nonasubstituted by identical or different halogens, C₁-C₆-acyl,C₁-C₆-acyloxy, C₁-C₆-alkoxycarbonyl, amino, which is optionally mono- ordisubstituted by identical or different substituents from the groupconsisting of C₁-C₄-alkyl and aryl, or represent C₆-C₁₀-aryl, which isoptionally mono- or polysubstituted by identical or differentsubstituents from the group consisting of halogen, cyano, nitro,C₁-C₅-alkyl, which is optionally mono- to hexasubstituted by identicalor different halogens, C₁-C₅-alkoxy, which is optionally mono- tohexasubstituted by identical or different halogens, C₁-C₅-alkylthio,which is optionally mono- to hexasubstituted by identical or differenthalogens, amino, monoalkylamino having straight-chain or branchedC₁-C₆-alkyl radicals, dialkylamino having identical or differentstraight-chain or branched C₁-C₆-alkyl radicals.

[0020] Particular preference is given to using compounds of the formula(I) in which R¹ and R² independently of one another each representhydrogen, fluorine, chlorine, bromine, cyano, nitro, or represent ineach case straight-chain or branched C₁-C₆-alkyl, C₂-C₆-alkenyl orC₂-C₆-alkinyl, each of which is optionally mono- to tetrasubstituted byidentical or different substituents from the group consisting offluorine, chlorine, bromine, nitro, cyano, phenyl, naphthyl, phenyloxy,naphthyloxy, C₁-C₄-alkoxy, which is optionally mono- to heptasubstitutedby identical or different substituents from the group consisting offluorine, chlorine, bromine, C₁-C₄-alkylthio, which is optionally mono-to heptasubstituted by identical or different substituents from thegroup consisting of fluorine, chlorine and bromine, C₁-C₄-acyl,C₁-C₄-alkoxy-carbonyl, amino, which is optionally mono- or disubstitutedby identical or different substituents from the group consisting ofC₁-C₄-alkyl, phenyl and naphthyl, or represent phenyl or naphthyl, eachof which is optionally mono- to tetrasubstituted by fluorine, chlorine,bromine, cyano, nitro, C₁-C₄-alkyl, which is optionally mono- totetrasubstituted by identical or different substituents from the groupconsisting of fluorine, chlorine and bromine, C₁-C₄-alkoxy, which isoptionally mono- to tetrasubstituted by identical or differentsubstituents from the group consisting of fluorine, chlorine andbromine, C₁-C₄-alkylthio, which is optionally mono- to tetrasubstitutedby identical or different substituents from the group consisting offluorine, chlorine and bromine, amino, monoalkylamino havingstraight-chain or branched C₁-C₄-alkyl radicals or dialkylamino havingidentical or different straight-chain or branched C₁-C₄-alkyl radicals.

[0021] Very particular preference is given to using compounds of theformula (I) in which R¹ and R² independently of one another eachrepresent hydrogen, fluorine, chlorine, bromine, cyano, nitro, methyl,ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl,represent in each case all isomers of pentyl, hexyl, heptyl and octyl,allyl, vinyl, propargyl, where the alkyl radicals mentioned are in eachcase optionally mono- to tetrasubstituted by identical or differentsubstituents from the group consisting of fluorine, chlorine, bromine,nitro, cyano, phenyl, phenoxy, 2,4-dichlorophenoxy, methoxy, ethoxy,n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy,trifluoromethoxy, methylthio, ethylthio, n-propylthio, isopropylthio,trifluoromethylthio, C₁-C₄-acyl, C₁-C₄-acyloxy, C₁-C₄-alkoxy-carbonyl,amino, which is optionally substituted by identical or differentradicals from the group consisting of C₁-C₄-alkyl, phenyl and naphthyl,furthermore represent phenyl or naphthyl, which are in each caseoptionally mono- to tetrasubstituted by identical or differentsubstituents from the group consisting of fluorine, chlorine, bromine,cyano, nitro, methyl, ethyl, n-propyl, isopropyl, trifluoromethyl,methoxy, ethoxy, n-propoxy, isopropoxy, trifluoromethoxy, methylthio,ethylthio, n-propylthio, isopropylthio, trifluoromethylthio, amino,methylamino, ethylamino, n-propylamino, isopropylamino, dimethylamino,diethylamino, methylethylamino, di-n-propylamino and di-isopropylamino.

[0022] Especially preferred is the use of compounds of the formula (I),in which R¹ represents hydrogen, fluorine, bromine, cyano, nitro,methyl, trifluoromethyl, difluoromethyl, methoxymethyl, ethoxymethyl,ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl,n-pentyl, n-hexyl, n-heptyl, n-octyl, allyl, vinyl, propargyl,phenoxymethyl, 2,4-dichlorophenoxymethyl or phenyl, which is optionallymono- to trisubstituted by identical or different substituents from thegroup consisting of fluorine, chlorine, bromine, cyano, nitro, methyl,ethyl, n-propyl, isopropyl, trifluoromethyl, methoxy, ethoxy, n-propoxy,isopropoxy, trifluoromethoxy, methylthio, ethylthio, n-propylthio,isopropylthio, trifluoromethylthio, amino, methylamino, ethylamino,n-propylamino, isopropylamino, dimethylamino, diethylamino,methylethylamino, di-n-propylamino and diisopropylamino and R²represents hydrogen.

[0023] Especially preferred is furthermore the use of compounds of theformula (I) in which

[0024] R¹ represents hydrogen, fluorine, bromine, cyano, nitro, methyl,trifluoromethyl, difluoromethyl, methoxymethyl, ethoxymethyl, ethyl,n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl,n-hexyl, n-heptyl, n-octyl, allyl, vinyl, propargyl, phenoxymethyl,2,4-dichlorophenoxymethyl or phenyl, which is optionally mono- totrisubstituted by identical or different substituents from the groupconsisting of fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl,n-propyl, isopropyl, trifluoromethyl, methoxy, ethoxy, n-propoxy,isopropoxy, trifluoromethoxy, methylthio, ethylthio, n-propylthio,isopropylthio, trifluoromethylthio, amino, methylamino, ethylamino,n-propylamino, isopropylamino, dimethylamino, diethylamino,methylethylamino, di-n-propylamino and diisopropylamino, and

[0025] R² represents hydrogen, fluorine, bromine, cyano, nitro, methyl,trifluoromethyl, difluoromethyl, methoxymethyl, ethoxymethyl, ethyl,n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl,n-hexyl, n-heptyl, n-octyl, allyl, vinyl, propargyl, phenoxymethyl orphenyl.

[0026] The radicals given in the respective definitions or the preferredand particularly preferred definitions can, independently of thecombination given in each case, also be replaced by any radicaldefinitions of other combinations. Moreover, radical definitions fromany preferred range may not apply.

[0027] The optionally substituted aryl radicals mentioned in thedefinition of R¹ and R² represent in particular in each case optionallysubstituted phenyl and naphthyl radicals.

[0028] The term halogen is to be understood as meaning in particularfluorine, chlorine and bromine.

[0029] The compounds of the formula (I) are novel and also form part ofthe subject-matter of the present invention, except for the compounds

[0030] methyl 3-nitro-isoxazole-5-carboxylate (CAS-RN: 40995-06-0)

[0031] ethyl 3-nitro-isoxazole-5-carboxylate (Beilstein RN : 6598833)

[0032] 3-nitro-5-phenylisoxazole (CAS-RN: 6455-30-7)

[0033] 3-nitro-5-methylisoxazole (CAS-RN: 750097-82-2)

[0034] 3-(3-nitro-isoxazol-5-yl)-prop-2-yn-1-ol (Beilstein RN: 1106231)

[0035] 3,5-dinitro-isoxazole (CAS-RN : 42216-62-6)

[0036] 4-methyl-3,5-dinitro-isoxazole (CAS-RN: 42216-63-7)

[0037] 3-nitro-5-(3-nitro-prop-1-ynyl)-isoxazole (Beilstein RN: 1119643)

[0038] 3-nitroisoxazole (CAS-RN: 39485-31-9)

[0039] 4-chloromethyl-3-nitro-isoxazole (Beilstein RN: 6594348)

[0040] 4-methyl-3-nitro-isoxazole (Beilstein RN: 6593345)

[0041] 5-butyl-3-nitro-isoxazole (CAS-RN: 40995-04-8)

[0042] 3-nitro-5-hydroxymethyl-isoxazole (CAS-RN: 75079-83-3)

[0043] 5-(brom-prop-1-ynyl)-3-nitro-isoxazole (CAS-RN: 40995-02-6)

[0044] 3-nitro-1-phenyl-isoxazole (Beilstein RN: 6596756)

[0045] (3-nitro-isoxazol-4-yl)-phenyl-methanone (Beilstein RN: 6599593)

[0046] 4-(4-methoxy-phenyl)-3-nitro-isoxazole (Beilstein RN: 6600205)

[0047] 3-nitro-4-(2-nitro-phenyl)-isoxazole (Beilstein RN: 6604179)

[0048] 3-nitro-4-(4-nitrophenyl)-isoxazole (Beilstein RN: 6604546)

[0049] 3-nitro-4-(2,4-dinitrophenyl)-isoxazole (Beilstein RN: 6612177)

[0050] 3-nitro-isoxazole-5-carbaldehyde (CAS-RN: 108802-81-9)

[0051] 3-nitro-5-acetyl-isoxazole (CAS-RN: 54468-91-6).

[0052] The novel and known 3-nitroisoxazoles of the formula (I) whichcan be used according to the invention are obtained when compounds ofthe formula (II)

R²—C≡C—R¹  (II)

[0053] in which

[0054] R¹ and R² are each as defined above

[0055] are reacted with tetranitroethylene, if appropriate in thepresence of diluents (see also K. Baum, J. Org. Chem. 1985, 50, 2736).

[0056] Suitable diluents which may be used, if appropriate, are allorganic solvents. These preferably include hydrocarbons, such astoluene, xylene or hexane, chlorinated hydrocarbons, such aschlorobenzene, methylene chloride or chloroform, ketones, such asacetone, ethers, such as tetrahydrofuran, diethyl ether, methyltert-butyl ether and dioxane, nitrites, such as acetonitrile, and alsoDMSO, DMF and NMP.

[0057] The reaction temperatures in this process can be varied within arelatively wide temperature range. In general, the process is carriedout at temperatures between −30° C. and +150° C., preferably between−10° C. and +50° C.

[0058] Tetranitroethylene can be prepared in a known manner fromhexanitroethane.

[0059] The compounds of the formula (II) used are known or can beprepared by generally known processes.

[0060] Nitroisoxazoles of the general formula (I) in which

[0061] R¹ is as defined above and

[0062] R² represents hydrogen

[0063] can alternatively can also be prepared by reacting compounds ofthe general formula (III)

X—CH₂—C≡C—R¹  (III)

[0064] in which

[0065] R¹ is as defined above and

[0066] X represents a leaving group, preferably bromine, iodine,chlorine, tosylate or mesylate,

[0067] with metal nitrites, preferably sodium nitrite or potassiumnitrite, if appropriate in the presence of diluents.

[0068] The reaction temperatures in this process can be varied within arelatively wide temperature range. In general, the process is carriedout at temperatures between −30° C. and +150° C., preferably between−10° C. and +80° C.

[0069] Suitable diluents which may be used, if appropriate, are bothwater and all organic solvents. These preferably include hydrocarbons,such as toluene, xylene or hexane, chlorinated hydrocarbons, such aschlorobenzene, methylene chloride or chloroform, ketones, such asacetone, ethers, such as tetrahydrofuran, diethyl ether, methyltert-butyl ether and dioxane, nitrites, such as acetonitrile, and alsoDMSO, DMF and NMP.

[0070] This process is suitable both for preparing the known compoundsof the formula (I) and the novel compounds of the formula (I) accordingto the invention, where the radical R¹ is as defined.

[0071] The substances of the formula (I) which can be used according tothe invention have potent microbicidal action and can be used forcontrolling undesirable microorganisms, such as fungi and bacteria, incrop protection and in the protection of materials.

[0072] In the protection of materials, the substances according to theinvention can be used for protecting industrial materials against attackand destruction by undesirable microorganisms. In the present context,industrial materials are to be understood as meaning non-live materialswhich have been prepared for use in industry. For example, industrialmaterials which are intended to be protected by active compoundsaccording to the invention from microbial change or destruction can beglues, sizes, paper and board, textiles, leather, wood, paints andsynthetic articles, cooling lubricants and other materials which can beattacked or destroyed by microorganisms. Parts of production plants, forexample cooling-water circuits, which may be impaired by themultiplication of microorganisms may also be mentioned in the context ofthe materials to be protected. Industrial materials which may preferablybe mentioned in the context of the present invention are glues, sizes,paper and boards, leather, wood, paints, cooling lubricants and heattransfer liquids.

[0073] Examples of microorganisms which are capable of bringing aboutdegradation of, or change in, the industrial materials and which may bementioned are bacteria, fungi, yeasts, algae and slime organisms. Theactive compounds according to the invention preferably act againstfungi, in particular molds, wood-discoloring and wood-destroying fungi(Basiidiomycetes) and also against slime organisms and bacteria.

[0074] Microorganisms of the following genera may be mentioned by way ofexample:

[0075] Alternaria, such as Alternaria tenuis,

[0076] Aspergillus, such as Aspergillus niger,

[0077] Chaetomium, such as Chaetomium globosum,

[0078] Coniophora, such as Coniophora puetana,

[0079] Lentinus, such as Lentinus tigrinus,

[0080] Penicillium, such as Penicillium glaucum,

[0081] Polyporus, such as Polyporus versicolor,

[0082] Aureobasidium, such as Aureobasidium pullulans,

[0083] Sclerophoma, such as Sclerophoma pityophila,

[0084] Trichoderma, such as Trichoderma viride,

[0085] Escherichia, such as Escherichia coli,

[0086] Pseudomonas, such as Pseudomonas aeruginosa,

[0087] Staphylococcus, such as Staphylococcus aureus.

[0088] The active compounds according to the invention, as such or intheir formulations, can also be used in a mixture with known fungicides,bactericides, acaricides, nematicides or insecticides, for example towiden the activity spectrum or to prevent the development of resistance.In many cases, synergistic effects are obtained, i.e. the activity ofthe mixture is greater than the activity of the individual components.

[0089] The following co-components are found to be particularlyfavorable:

[0090] triazoles such as:

[0091] azaconazole, azocyclotin, bitertanol, bromuconazole,cyproconazole, diclobutrazole, difenoconazole, diniconazole,epoxyconazole, etaconazole, fenbuconazole, fenchlorazole, fenethanil,fluquinconazole, flusilazole, flutriafol, furconazole, hexaconazole,imibenconazole, ipconazole, isozofos, myclobutanil, metconazole,paclobutrazol, penconazole, propioconazole,(±)-cis-1-(4-chlorophenyl)-2-(1H-1,2,4-triazol-1-yl)-cycloheptanol,2-(1-tert-butyl)-1-(2-chlorophenyl)-3-(1,2,4-triazol-1-yl)-propan-2-ol,tebuconazole, tetraconazole, triadimefon, triadimenol, triapenthenol,triflumizole, triticonazole, uniconazole and their metal salts and acidadducts;

[0092] imidazoles such as:

[0093] clotrimazole, bifonazole, climbazole, econazole, fenapamil,imazalil, isoconazole, ketoconazole, lombazole, miconazole, pefurazoate,prochloraz, triflumizole, thiazolcar,1-imidazolyl-1-(4′-chlorophenoxy)-3,3-dimethylbutan-2-one, and theirmetal salts and acid adducts;

[0094] pyridines and pyrimidines such as:

[0095] ancymidol, buthiobate, fenarimol, mepanipyrin, nuarimol,pyvoxyfur, triamirol;

[0096] succinate dehydrogenase inhibitors such as:

[0097] benodanil, carboxim, carboxim sulphoxide, cyclafluramid,fenfuram, flutanil, furcarbanil, furmecyclox, mebenil, mepronil,methfuroxam, metsulfovax, pyrocarbolid, oxycarboxin, shirlan, Seedvax;

[0098] naphthalene derivatives such as:

[0099] terbinafine, naftifine, butenafine,3-chloro-7-(2-aza-2,7,7-trimethyl-oct-3-en-5-ine);

[0100] sulfenamides such as:

[0101] dichlofluanid, tolylfluanid, folpet, fluorofolpet, captan,captofol;

[0102] Benzimidazoles such as:

[0103] carbendazim, benomyl, fuberidazole, thiabendazole or their salts;

[0104] morpholine derivatives such as:

[0105] aldimorph, dimethomorph, dodemorph, falimorph, fenpropidinfenpropimorph, tridemorph, trimorphamid and their arylsulphonate saltssuch as, for example, p-toluenesulphonic acid andp-dodecylphenyl-sulphonic acid;

[0106] benzothiazoles such as:

[0107] 2-mercaptobenzothiazole;

[0108] benzothiophene dioxides such as:

[0109] N-cyclohexyl-benzo[b]thiophene-S,S-dioxide carboxamide;

[0110] benzamides such as:

[0111] 2,6-dichloro-N-(4-trifluoromethylbenzyl)-benzamide, tecloftalam;

[0112] boron compounds such as:

[0113] boric acid, boric ester, borax;

[0114] formaldehyde and formaldehyde-releasing compounds such as:

[0115] benzyl alcohol mono-(poly)-hemiformal, n-butanol hemiformal,dazomet, ethylene glycol hemiformal, hexa-hydro-S-triazine,hexamethylenetetramine, N-hydroxymethyl-N′-methylthiourea,N-methylolchloroacetamide, oxazolidine, paraformaldehyde, taurolin,tetrahydro-1,3-oxazine, N-(2-hydroxypropyl)-amine-methanol;

[0116] isothiazolinones such as:

[0117] N-methylisothiazolin-3-one, 5-chloro-N-methylisothiazolin-3-one,4,5-dichloro-N-octylisothiazolin-3-one, 5-chloro-N-octylisothiazolinone,N-octylisothiazolin-3-one, 4,5-trimethylene-isothiazolinone,4,5-benzoisothiazolinone;

[0118] aldehydes such as:

[0119] cinnamaldehyde, formaldehyde, glutardialdehyde,β-bromocinnamaldehyde;

[0120] thiocyanates such as:

[0121] thiocyanatomethylthiobenzothiazole, methylenebisthiocyanate;

[0122] quaternary ammonium compounds such as:

[0123] benzalkonium chloride, benzyldimethyltetradecylammonium chloride,benzyldimethyldodecylammonium chloride,dichlorobenzyl-dimethyl-alkyl-ammonium chloride, didecyldimethylammoniumchloride, dioctyl-dimethyl-ammonium chloride,N-hexadecyl-trimethyl-ammonium chloride, 1-hexadecyl-pyridiniumchloride, iminoctadine tris (albesilate);

[0124] iodine derivatives such as:

[0125] diiodomethyl p-tolyl sulphone, 3-iodo-2-propinyl alcohol,4-chlorophenyl-3-iodopropargylformal, 3-bromo-2,3-diiodo-2-propenylethylcarbamate, 2,3,3-triiodoallyl alcohol,3-bromo-2,3-diiodo-2-propenyl alcohol, 3-iodo-2-propinyln-butylcarbamate, 3-iodo-2-propinyl n-hexylcarbamate,3-iodo-2-propinyl-cyclohexylcarbamate, 3-iodo-2-propinylphenylcarbamate;

[0126] phenols such as:

[0127] tribromophenol, tetrachlorophenol, 3-methyl-4-chlorophenol,3,5-dimethyl-4-chlorophenol, phenoxyethanol, dichlorophene,2-benzyl-4-chlorophenol, 5-chloro-2-(2,4-dichlorophenoxy)-phenol,hexachlorophene, p-hydroxybenzoate, o-phenylphenol, m-phenylphenol,p-phenylphenol and their alkali metal salts and alkaline earth metalsalts;

[0128] microbicides with an activated halogen group such as: bronidox,2-bromo-2-nitro-1,3-propanediol, 2-bromo-4′-hydroxy-acetophenone,1-bromo-3-chloro-4,4,5,5-tetramethyl-2-imidazolidinone,β-brom-β-nitrostyrene, chloracetamid, chloramin T,1,3-dibromo-4,4,5,5-tetramethyl-2-imidazolidinone, dichloramin T,3,4-dichloro-(3H)-1,2-dithiol-3-one, 2,2-dibromo-3-nitrile-propionamide,1,2-dibromo-2,4-dicyanobutane, halane, halazone, mucochloric acid,phenyl (2-chlorocyano-vinyl) sulphone, phenyl(1,2-dichloro-2-cyanovinyl) sulphone, trichloroisocyanuric acid;

[0129] pyridines such as:

[0130] 1-hydroxy-2-pyridinethione (and their Na, Fe, Mn, Zn salts),tetrachloro-4-methylsulphonylpyridine, pyrimethanol, mepanipyrim,dipyrithion, 1-hydroxy-4-methyl-6-(2,4,4-trimethylpentyl )-2(1H)-pyridine;

[0131] methoxyacrylates or similar such as:

[0132] azoxystrobin, methyl(E)-methoximino[alpha-(o-tolyloxy)-o-tolyl]acetate,(E)-2-methoxyimino-N-methyl-2-(2-phenoxyphenyl)acetamide,(E)-2-{2-[6-(2-cyanophenoxy)pyrimidin-4-yloxy]phenyl}-3-methoxyacrylate,O-methyl2-[([3-methoximino-2-butyl)imino]oxy)o-tolyl]-2-methoximino-acetimidate,2-[[[[1-(2,5-dimethylphenyl)ethylidene]amino]oxy]methyl]-alpha-(methoximino)-N-methylbenzeneacetamide,alpha-(methoxyimino)-N-methyl-2-[[[[1-[3-(trifluoromethyl)phenyl]ethylidene]amino]oxy]methyl]-benzeneacetamide,trifluoxystrobin,alpha-(methoxymethylene)-2-[[[[1-[3-(trifluoromethyl)phenyl]ethylidene]amino]oxy]methyl]-benzeneaceticacid methyl ester,2-[[[5-chloro-3-(trifluoromethyl)-2-pyridinyl]oxy]methyl]-alpha-(methoxyimino)-N-methylbenzeneacetamide,2-[[[cyclopropyl[(4-ethoxyphenyl)imino]methyl]thio]methyl]-alpha-(methoxyimino)-benzeneaceticacid methyl ester,alpha-(methoxyimino)-N-methyl-2-(4-methyl-5-phenyl-2,7-dioxa-3,6-diazaocta-3,5-dien-1-yl)-benzeneacetamide,alpha-(methoxymethylene)-2-(4-methyl-5-phenyl-2,7-dioxa-3,6-diazaocta-3,5-dien-1-yl)-benzeneaceticacid methyl ester,alpha-(methoxyimino)-N-methyl-2-[[[1-[3-(trifluoromethyl)phenyl]ethoxy]-imino]methyl]-benzeneacetamide,2-[[(3,5-dichloro-2-pyridinyl)oxy]methyl]-alpha-(methoxyimino)-N-methyl-benzeneacetamide,2-[4,5-dimethyl-9-(4-morpholinyl)-2,7-dioxa-3,6-diazanona-3,5-dien-1-yl]-alpha-(methoxymethylene)-benzeneaceticacid methyl ester, kresoxim-methyl;

[0133] metal soaps such as: tin naphthenate, tin octoate, tin2-ethylhexanoate, tin oleate, tin phosphate, tin benzoate, coppernaphthenate, copper octoate, copper 2-ethylhexanoate, copper oleate,copper phosphate, copper benzoate, zinc naphthenate, zinc octoate, zinc2-ethylhexanoate, zinc oleate, zinc phosphate, zinc benzoate;

[0134] metal salts such as: copper hydroxycarbonate, sodium dichromate,potassium dichromate, potassium chromate, copper sulphate, copperchloride, copper borate, zinc fluorosilicate, copper fluorosilicate;

[0135] oxides such as: tributyltin oxide, Cu₂O, CuO, ZnO;

[0136] dithiocarbamates such as: cufraneb, ferban, potassiumN-hydroxymethyl-N′-methyl-dithiobarbamate, sodiumdimethyldithiocarbamate, potassium dimethyldithiocarbamate, macozeb,maneb, metam, metiram, thiram, zineb, ziram;

[0137] nitriles such as:

[0138] 2,4,5,6-tetrachloroisophthalonitrile, disodiumcyano-dithioimidocarbamate;

[0139] quinolines such as:

[0140] 8-hydroxyquinoline and their copper salts;

[0141] other fungicides and bactericides such as:

[0142] 5-hydroxy-2(5H)-furanone, 4,5-benzodithiazolinone,4,5-trimethylenedithiazolinone, N-(2-p-chlorobenzoylethyl)-hexaminiumchloride, 2-oxo-2-(4-hydroxy-phenyl)acetohydroxycinnamoyl chloride,tris-N-(cyclohexyldiazeniumdioxy)-aluminium,N-(cyclo-hexyldiazeniumdioxy)-tributyltin or its potassium salts,bis-N-(cyclohexyldiazeniumdioxy)-copper; iprovalicarb, fenhexamid,spiroxamine, carpropamid, diflumetorin, quinoxyfen, famoxadone,polyoxorim, acibenzolar S-methyl, furametpyr, trifluzamide, methalaxy-M,Ag-, Zn- or Cu-containing zeolites alone or incorporated into polymericmaterials.

[0143] Very especially preferred are mixtures of compounds of the formla(I) with one or more of the following active compounds:

[0144] azaconazole, bromuconazole, cyproconazole, dichlobutrazol,diniconazole, hexaconazole, metaconazole, penconazole, propiconazole,tebuconazole, dichlofluanid, tolylfluanid, fluorfolpet, methfuroxam,carboxin, benzo[b]thiophene S,S-dioxide N-cyclohexylcarboxamide,fenpiclonil,4-(2,2-difluoro-1,3-benzodioxol-4-yl)-1H-pyrrole-3-carbonitrile,butenafine, imazalil, N-methyl-isothiazolin-3-one,5-chloro-N-methylisothiazolin-3-one, N-octylisothiazolin-3-one,dichloro-N-octylisothiazolinone, mercaptobenthiazole,thiocyanatomethylthiobenzothiazole, benzoisothiazolinone,N-(2-hydroxypropyl)-amino-methanol, benzyl alcohol (hemi)-formal,N-methylolchloroacetamide, N-(2-hydroxypropyl)-amine-methanol,glutaraldehyde, omadine, dimethyl dicarbonate,2-bromo-2-nitro-1,3-propanediol and/or 3-iodo-2-propinyln-butylcarbamate.

[0145] Apart from with the abovementioned fungicides and bactericides,mixtures with a good efficacy are, moreover, also prepared with otheractive compounds:

[0146] insecticides/acaricides/nematicides such as:

[0147] abamectin, acephate, acetamiprid, acrinathrin, alanycarb,aldicarb, aldoxycarb, aldrin, allethrin, alpha-cypermethrin, amitraz,avermectin, AZ 60541, azadirachtin, azinphos A, azinphos M, azocyclotin,Bacillus thuringiensis, barthrin,4-bromo-2(4-chlorophenyl)-1-(ethoxymethyl)-5-(trifluoromethyl)-1H-pyrrole-3-carbonitrile,bendiocarb, benfuracarb, bensultap, betacyfluthrin, bifenthrin,bioresmethrin, bioallethrin, bromophos A, bromophos M, bufencarb,buprofezin, butathiophos, butocarboxim, butoxycarboxim, cadusafos,carbaryl, carbofuran, carbophenothion, carbosulfan, cartap,quinomethionate, cloethocarb, chlordane, chlorethoxyfos, chlorfenapyr,chlorfenvinphos, chlorfluazuron, chlormephos,N-[(6-chloro-3-pyridinyl)-methyl]-N′-cyano-N-methyl-ethaneimidamide,chlorpicrin, chlorpyrifos A, chlorpyrifos M, cisresmethrin, clocythrin,cypophenothrin clofentezin, coumaphos, cyanophos, cycloprothrin,cyfluthrin, cyhalothrin, cyhexatin, cypermethrin, cyromazin,decamethrin, deltamethrin, demeton M, demeton S, demeton-S-methyl,diafenthiuron, dialiphos, diazinon,1,2-dibenzoyl-1(1,1-dimethyl)-hydrazine, DNOC, dichlofenthion,dichlorvos, dicliphos, dicrotophos, difethialone, diflubenzuron,dimethoate, dimethyl-(phenyl)-silyl-methyl 3-phenoxybenzyl ether,dimethyl-(4-ethoxyphenyl)-silylmethyl-3-phenoxybenzyl ether,dimethylvinphos, dioxathion, disulfoton, eflusilanate, emamectin,empenthrin, endosulfan, EPN, esfenvalerate, ethiofencarb, ethion,ethofenprox, etrimphos, etoxazole, etobenzanid, fenamiphos, fenazaquin,fenbutatin oxide, fenfluthrin, fenitrothion, fenobucarb, fenothiocarb,fenoxycarb, fenpropathrin, fenpyrad, fenpyroximat, fensulfothion,fenthion, fenvalerate, fipronil, fluazuron, flucycloxuron,flucythrinate, flufenoxuron, flupyrazotos, flufenzine, flumethrin,flufenprox, fluvalinate, fonophos, formethanate, formothion, fosmethilanfosthiazate, fubfenprox, furathiocarb, halofenocid, HCH, heptenophos,hexaflumuron, hexythiazox, hydramethylnon, hydroprene, imidacloprid,imiprothrin, indoxycarb, iodfenfos, iprinomectin, iprobenfos, isazophos,isoamidophos, isofenphos, isoprocarb, isoprothiolane, isoxathion,ivermectin, lama-cyhalothrin, lufenuron, kadedrin lambda-cyhalothrin,lufenuron, malathion, mecarbam, mervinphos, mesulfenphos, metaldehyde,methacrifos, methamidophos, methidathion, methiocarb, methomyl,metalcarb, milbemectin, monocrotophos, moxiectin, naled, NC 184, NI 125,nicotine, nitenpyram, omethoate, oxamyl, oxydemethon M, oxydeprofos,parathion A, parathion M, penfluron, permethrin,2-(4-phenoxyphenoxy)-ethyl ethylcarbamate, phenthoate, phorate,phosalon, phosmet, phosphamidon, phoxim, pirimicarb, pirimiphos M,pirimiphos A, prallethrin, profenophos, promecarb, propaphos, propoxur,prothiophos, prothoate, pymetrozin, pyrachlophos, pyridaphenthion,pyresmethrin, pyrethrum, pyridaben, pyrimidifen, pyriproxifen,pyrithiobac-sodium, quinalphos, resmethrin, RH-7988, rotenone,salithion, sebufos, silafluofen, spinosad, sulfotep, sulprofos,tau-fluvalinate, taroils, tebufenozide, tebufenpyrad, tebupirimphos,teflubenzuron, tefluthrin, temephos, terbam, terbufos,tetrachlorvinphos, tetramethrin, Tetramethacarb, thiacloprid, thiafenox,thiamethoxam, thiapronil, thiodicarb, thiofanox, thiazophos, thiocyclam,thiomethon, thionazin, thuringiensin, tralomethrin, transfluthrin,triarathen, triazophos, triazamate, trichlorfon, triflumuron,trimethacarb, vamidothion, XMC, xylylcarb, zetamethrin;

[0148] molluscicides such as:

[0149] fentin acetate, metaldehyde, methiocarb. miclosamide;

[0150] Herbicides and other algicides such as acetochlor, acifluorfen,aclonifen, acrolein, alachlor, alloxydim, ametryn, amidosulfuron,amitrole, ammonium sulphamate, anilofos, asulam, atrazine, azafenidin,aziptrotryne, azimsulfuron, benazolin, benfluralin, benfuresate,bensulfuron, bensulphide, bentazone, benzofencap, benzthiazuron,bifenox, bispyribac, bispyribac-sodium, bispyribac-methyl, borax,bromacil, bromobutide, bromofenoxim, bromoxynil, butachlor, butamifos,butralin, butylate, bialaphos, benzoyl-prop, bromobutide, butroxydim,carbetamide, carfentrazone-ethyl, carfenstrole, chlomethoxyfen,chloramben, chlorbromuron, chlorflurenol, chloridazon, chlorimuron,chlornitrofen, chloroacetic acid, chloransulam-methyl, cinidon-ethyl,chlorotoluron, chloroxuron, chlorpropham, chlorsulfuron, chlorthal,chlorthiamid, cinmethylin, cinofulsuron, clefoxydim, clethodim,clomazone, chlomeprop, clopyralid, cyanamide, cyanazine, cycloate,cycloxydim, chloroxynil, clodinafop-propargyl, cumyluron, clometoxyfen,cyhalofop, cyhalofop-butyl, clopyrasuluron, cyclosulfamuron, diclosulam,dichlorprop, dichlorprop-P, diclofop, diethatyl, difenoxuron,difenzoquat, diflufenican, diflufenzopyr, dimefuron, dimepiperate,dimethachlor, dimethipin, dinitramine, dinoseb, dinoseb acetate,dinoterb, diphenamid, dipropetryn, diquat, dithiopyr, diduron, DNOC,DSMA, 2,4-D, daimuron, dalapon, dazomet, 2,4-DB, desmedipham, desmetryn,dicamba, dichlobenil, dimethamid, dithiopyr, dimethametryn, eglinazine,endothal, EPTC, esprocarb, ethalfluralin, ethidimuron, ethofumesate,ethobenzanid, ethoxyfen, ethametsulfuron, ethoxysulfuron, fenoxaprop,fenoxaprop-P, fenuron, flamprop, flamprop-M, flazasulfuron, fluazifop,fluazifop-P, fuenachlor, fluchloralin, flufenacet, flumeturon,fluorocglycofen, fluoronitrofen, flupropanate, flurenol, fluridone,flurochloridone, fluroxypyr, fomesafen, fosamine, fosametine,flamprop-isopropyl, flamprop-isopropyl-L, flumiclorac-pentyl,flumipropyn, flumioxzim, flurtamone, flumioxzim, flupyrsulfuron-methyl,fluthiacet-methyl, glyphosate, glufosinate-ammonium haloxyfop,hexazinone, imazamethabenz, isoproturon, isoxaben, isoxapyrifop,imazapyr, imazaquin, imazethapyr, ioxynil, isopropalin, imazosulfuron,imazomox, isoxaflutole, imazapic, lactofen, lenacil, linuron, MCPA,MCPA-thioethyl, MCPB, mecoprop, mecoprop-P, mefenacet, mefluidide,metam, metamitron, metazachlor, methabenzthiazuron, methazole,methoropytryne, methyldymron, methyl isothiocyanate, metobromuron,metoxuron, metribuzin, metsulfuron, molinate, manolide, monolinuron,MSMA, metolachlor, metosulam, metobenzuron, naproanilide, napropamide,naptalam, neburon, nicosulfuron, norflurazon, sodium chlorate,oxadiazon, oxyfluorfen, oxysulfuron, orbencarb, oryzalin, oxadiargyl,propyzamide, prosulfocarb, pyrazolate, pyrazolsulfuron, pyrazoxyfen,pyribenzoxium, pyributicarb, pyridate, paraquat, pebulate,pendimethalin, pentachlorophenol, pentoxazone, pentanochlor, petroleumoils, phenmedipham, picloram, piperophos, pretilachlor, primisulfuron,prodiamine, prometryn, propachlor, propanil, propaquizafob, propazine,propham, proisochlor, pyriminobac-methyl, pelargonic acid, pyrithiobac,pyraflufen-ethyl, quinmerac, quinocloamine, quizalofop, quizalofop-P,quinchlorac, rimsulfuron sethoxydim, sifuron, simazine, simetryn,sulfosulfuron, sulfometuron, sulfentrazone, sulcotrione, sulfosate, taroils, TCA, tebutam, tebuthiuron, terbacil, terbumeton, terbuthylazine,terbutryn, thiazafluoron, thifensulfuron, thiobencarb, thiocarbazil,tralkoxydim, tri-allate, triasulfuron, tribenuron, triclopyr,tridiphane, trietazine, trifluoralin, tycor, thdiazimin, thiazopyr,triflusulfuron, vernolate.

[0151] Depending on their physical properties and/or chemicalproperties, the active compounds of the formula (I) can be convertedinto customary formulations, such as solutions, emulsions, suspensions,powders, foams, pastes, granules, aerosols and microencapsulations inpolymeric substances.

[0152] The formulations or compositions are prepared in a manner knownper se, for example by mixing the active compounds with extenders, i.e.liquid solvents or other carriers, using, if appropriate, surfactants,i.e. emulsifiers and/or dispersants and/or foam-formers. Suitableemulsifiers and/or foam-formers are: for example nonionic and anionicemulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylenefatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkyl sulphates, aryl sulphonates, and also proteinhydrolysates; suitable dispersants are: for example lignosulphite wasteliquors and methyl cellulose. Tackifiers, such as carboxymethylcellulose, natural and synthetic polymers in the form of powders,granules or latices, such as gum arabic, polyvinyl alcohol and polyvinylacetate, and also natural phospholipids, such as cephalins andlecithins, and synthetic phospholipids can be used in the formulations.Other possible additives are mineral oils and vegetable oils.

[0153] The compositions used for protecting industrial materialsgenerally comprise the active compounds in an amount of from 1 to 95%,preferably from 10 to 75%.

[0154] The use concentrations of the active compounds according to theinvention depend on the type and the occurrence of the microorganisms tobe controlled, and on the composition of the material to be protected.The optimal rate can be determined by test series. In general, the useconcentrations are in the range from 0.001 to 5% by weight, preferablyfrom 0.05 to 1.0% by weight, based on the material to be protected.

[0155] The invention is further described in the following illustrativeexamples in which all parts and percentages are by weight unlessotherwise indicated.

PREPARATION EXAMPLES Example 1

[0156] 3-Nitroisoxazole

[0157] 20.7 g (0.3 mol) of sodium nitrite were initially charged in 100ml of DMF and, with cooling, treated dropwise with 22.3 g (0.15 mol) ofan 80% strength solution of propargyl bromide. The color of the reactionsolution changed to dark violet. The mixture was stirred at roomtemperature for 24 h and then poured into 300 ml of water and extractedtwice with ether, and the extract was washed with saturated NaClsolution, dried over sodium sulfate and concentrated. The brown residuewas chromatographed on silica gel (toluene). This gave 1.66 g of3-nitroisoxazole as a pale yellow oil having the physical data given inTable 1.

[0158] The compounds listed in Table 1 were prepared similarly toExample 1 and the processes mentioned in the description. TABLE 1Compounds of the general formula (I) Example R¹ R² Physical data 1 H H¹H-NMR(CDCl₃)δ = 6.99(d, 1H), 8.66(d, 1H) 2 —C₆H₅ H Mp = 98-102° C. 3—CH₃ H ¹H-NMR(CDCl₃)δ = 2.6(s, 3H), 6.6(s, 1H) 4 —C₄H₉ H ¹H-NMR(CDCl₃)δ= 0.95(t, 3H), 1.42(m, 2H), 1,74(m, 2H), 2.85(t, 2H), 6.60(s, 1H) 5

H Mp = 88° C. 6 —C₇H₁₅ H ¹H-NMR(CDCl₃)δ = 0.9(t, 3H), 1.2-1.4(m, 8H),1.75(m, 2H), 2.85 (t, 2H), 6.5(s, 1H) 7 —CH₂OH H ¹H-NMR(CDCl₃)δ = 2.4(s,1H), 4.9(d, 2H), 6.9(s, 1H)

Use Example A

[0159] To demonstrate the activity against bacteria, the minimuminhibitory concentrations (MIC) of the agents according to the inventionare determined:

[0160] A defined Landy agar is admixed with active compounds accordingto the invention in concentrations of from 0.1 mg/ml to 5000 mg/ml.After the agar has solidified, it is inoculated with pure cultures ofthe test organisms listed in Table 2. The MIC is determined after 3 daysof storage at 28° C. and 60-70% relative atmospheric humidity. The MICis the lowest concentration of active compound at which there is nocolonization by the microbial species used, it is stated in the tablebelow. TABLE 2 Minimum inhibitory concentration (ppm) of compounds ofthe formula (I) according to the invention Example No. Pseudomonasaeroginosa Bacillus subtilis 1 100 <40 2 >400 <40 3 200 <40 4 200 <405 >400 <40 8 100 <40

Use Example B

[0161] To demonstrate the activity against fungi, the minimum inhibitoryconcentrations (MIC) of the agents according to the invention aredetermined:

[0162] An agar which has been prepared using malt extract is admixedwith active compounds according to the invention in concentrations offrom 0.1 mg/ml to 5000 mg/ml. After the agar has solidified, it isinoculated with pure cultures of the test organisms listed in Table 3.The MIC is determined after 2 weeks of storage at 28° C. and 60-70%relative atmospheric humidity. The MIC is the lowest concentration ofactive compound at which there is no colonization by the microbialspecies used, it is stated in Table 3 below. TABLE 3 Minimum inhibitoryconcentration (ppm) of compounds of the formula (I) according to theinvention Penicillium Chaetomium Aspergillus Example No. brevicauleglobusum niger 1 100 200 100 2 200 200 400 3 200 200 200 4 400 400 >4005 200 100 400 8 100 200 200

[0163] Although the present invention has been described in detail withreference to certain preferred versions thereof, other variations arepossible. Therefore, the spirit and scope of the appended claims shouldnot be limited to the description of the versions contained therein.

What is claimed is:
 1. A method comprising treating a microbe or ahabitat of the microbe with a compound and allowing the compound to acton the microbe or its habitat, wherein the compound is of formula (I):

wherein R¹ and R² independently of one another each represent hydrogen,halogen, nitro, cyano, or represent in each case an optionallysubstituted alkyl, alkenyl, alkinyl or aryl.
 2. The method according toclaim 1, wherein in formula (I), R¹ and R² independently of one anothereach represent hydrogen, halogen, cyano, nitro, or represent in eachcase straight-chain or branched C₁-C₈-alkyl, C₂-C₈-alkenyl orC₂-C₈-alkinyl, each of which is optionally mono- or polysubstituted byidentical or different substituents selected from the group consistingof halogens, nitros, cyanos, aryls, aryloxy groups, or C₁-C₆-alkoxygroups, each substituent which is optionally mono- to nonasubstituted byidentical or different halogens, C₁-C₆-alkylthio, which is optionallymono- to nonasubstituted by identical or different halogens, C₁-C₆-acyl,C₁-C₆-acyloxy, C₁-C₆-alkoxy-carbonyl, amino, which is optionally mono-or disubstituted by identical or different substituents from the groupconsisting of C₁-C₄-alkyl and aryl, or represent C₆-C₁₀-aryl, which isoptionally mono- or polysubstituted by identical or differentsubstituents from the group consisting of halogen, cyano, nitro,C₁-C₅-alkyl, which is optionally mono- to hexasubstituted by identicalor different halogens, C₁-C₅-alkoxy, which is optionally mono- tohexasubstituted by identical or different halogens, C₁-C₅-alkylthio,which is optionally mono- to hexasubstituted by identical or differenthalogens, amino, monoalkylamino having straight-chain or branchedC₁-C₆-alkyl radicals, dialkylamino having identical or differentstraight-chain or branched C₁-C₆-alkyl radicals.
 3. The method accordingto claim 1, wherein in formula (I), wherein R¹ and R² independently ofone another each represent hydrogen, fluorine, chlorine, bromine, cyano,nitro, or represent in each case straight-chain or branched C₁-C₆-alkyl,C₂-C₆-alkenyl or C₂-C₆-alkinyl, each of which is optionally mono- totetrasubstituted by identical or different substituents from the groupconsisting of fluorine, chlorine, bromine, nitro, cyano, phenyl,naphthyl, phenyloxy, naphthyloxy, C₁-C₄-alkoxy, which is optionallymono- to heptasubstituted by identical or different substituents fromthe group consisting of fluorine, chlorine, bromine, C₁-C₄-alkylthio,which is optionally mono- to heptasubstituted by identical or differentsubstituents from the group consisting of fluorine, chlorine andbromine, C₁-C₄-acyl, C₁-C₄-alkoxy-carbonyl, amino, which is optionallymono- or disubstituted by identical or different substituents from thegroup consisting of C₁-C₄-alkyl, phenyl and naphthyl, or representphenyl or naphthyl, each of which is optionally mono- totetrasubstituted by fluorine, chlorine, bromine, cyano, nitro,C₁-C₄-alkyl, which is optionally mono- to tetrasubstituted by identicalor different substituents from the group consisting of fluorine,chlorine and bromine, C₁-C₄-alkoxy, which is optionally mono- totetrasubstituted by identical or different substituents from the groupconsisting of fluorine, chlorine and bromine, C₁-C₄-alkylthio, which isoptionally mono- to tetrasubstituted by identical or differentsubstituents from the group consisting of fluorine, chlorine andbromine, amino, monoalkylamino having straight-chain or branchedC₁-C₄-alkyl radicals or dialkylamino having identical or differentstraight-chain or branched C₁-C₄-alkyl radicals.
 4. The method of claim1, wherein the compound of the formula (I) treats a microbe on anindustrial material or plant and protects the industrial material or theplant.
 5. The method of claim 1, wherein the compound of the formula (I)treats an industrial material and protects the material against fungiand bacteria.
 6. A microbicidal composition comprising: (A) a compoundof the formula (I)

 wherein R¹ and R² independently of one another each represent hydrogen,halogen, nitro, cyano, or represent in each case an optionallysubstituted alkyl, alkenyl, alkinyl or aryl, (B) solvents or diluentsand, (C) optionally processing auxiliaries, or active compounds, ormixtures thereof.
 7. A process for preparing a microbicidal compositioncomprising: (A) a compound of the formula (I)

 wherein R¹ and R² independently of one another each represent hydrogen,halogen, nitro, cyano, or represent in each case an optionallysubstituted alkyl, alkenyl, alkinyl or aryl, (B) solvents or diluentsand, (C) optionally processing auxiliaries, or active compounds, ormixtures thereof, the process comprising mixing (i) a compound of theformula (I)

 wherein R¹ and R² independently of one another each represent hydrogen,halogen, nitro, cyano, or represent in each case an optionallysubstituted alkyl, alkenyl, alkinyl or aryl, with (ii) solvents or (iii)diluents and, optionally (iii) with processing auxiliaries, activecompounds, or mixtures thereof.
 8. An industrial material comprising acompound of the formula (I)

wherein R¹ and R² independently of one another each represent hydrogen,halogen, nitro, cyano, or represent in each case an optionallysubstituted alkyl, alkenyl, alkinyl or aryl.
 9. A compound of theformula (I)

wherein R¹ and R² independently of one another each represent hydrogen,halogen, nitro, cyano or represent in each case optionally substitutedalkyl, alkenyl, alkinyl or aryl, except for methyl3-nitro-isoxazole-5-carboxylate (CAS-RN: 40995-06-0) ethyl3-nitro-isoxazole-5-carboxylate (Beilstein RN : 6598833)3-nitro-5-phenylisoxazole (CAS-RN: 6455-30-7) 3-nitro-5-methylisoxazole(CAS-RN: 750097-82-2) 3-(3-nitro-isoxazol-5-yl)-prop-2-yn-1-ol(Beilstein RN: 1106231) 3,5-dinitro-isoxazole (CAS-RN : 42216-62-6)4-methyl-3,5-dinitro-isoxazole (CAS-RN: 42216-63-7)3-nitro-5-(3-nitro-prop-1-ynyl)-isoxazole (Beilstein RN: 1119643)3-nitroisoxazole (CAS-RN: 39485-31-9) 4-chloromethyl-3-nitro-isoxazole(Beilstein RN: 6594348) 4-methyl-3-nitro-isoxazole (Beilstein RN:6593345) 5-butyl-3-nitro-isoxazole (CAS-RN: 40995-04-8)3-nitro-5-hydroxymethyl-isoxazole (CAS-RN: 75079-83-3)5-(bromo-prop-1-ynyl)-3-nitro-isoxazole (CAS-RN: 40995-02-6)3-nitro-1-phenyl-isoxazole (Beilstein RN: 6596756)(3-nitro-isoxazol-4-yl)-phenyl-methanone (Beilstein RN: 6599593)4-(4-methoxy-phenyl)-3-nitro-isoxazole (Beilstein RN: 6600205)3-nitro-4-(2-nitro-phenyl)-isoxazole (Beilstein RN: 6604179)3-nitro-4-(4-nitrophenyl)-isoxazole (Beilstein RN: 6604546)3-nitro-4-(2,4-dinitrophenyl)-isoxazole (Beilstein RN: 6612177)3-nitro-isoxazole-5-carbaldehyde (CAS-RN: 108802-81-9)3-nitro-5-acetyl-isoxazole (CAS-RN: 54468-91-6).
 10. A process forpreparing a compound of the formula (I)

wherein R¹ and R² independently of one another each represent hydrogen,halogen, nitro, cyano, or represent in each case an optionallysubstituted alkyl, alkenyl, alkinyl or aryl, the process comprisingreacting (i) a compound of the formula (II) R²—C≡C—R¹  (II)  wherein R¹and R² are each as defined above with (ii) tetranitroethylene,optionally in the presence of a diluent.
 11. A process for preparing acompound of the formula (I)

wherein R¹ is hydrogen, halogen, nitro, cyano, or represent in each casean optionally substituted alkyl, alkenyl, alkinyl or aryl, R² representshydrogen, the process comprising reacting (i) a compound of the generalformula (III) X—CH₂—C≡C—R¹  (III) in which R¹ is as defined above and Xrepresents a leaving group, preferably bromine, iodine, chlorine,tosylate or mesylate with (ii) metal nitrites, optionally, in thepresence of diluents.
 12. The process of claim 11, wherein the nitritesare selected from the group consisting of sodium nitrite and potassiumnitrite.